Patent GB-645901-A (GB)
Title: Thio-ether substituted thiazoles and selenazoles and process of preparing the same
IPC: C07D277/54
Filed: 1948-03-22
Abstract: Compounds of the general formula <FORM:0645901/IV (b)/1> wherein R is an amino, alkyl, aryl, aralkyl, or heterocyclic group, R1 and R2 are alkyl, aryl, aralkyl, or heterocyclic groups, and Y is S or Se are prepared by heating together molecular equivalents of a halogenated ketonyl thioether, and thiourea, selenourea, a thioacylamide, or a selenoacylamide.  2 : 4 - Dimethyl-5-ethylmercaptothiazole is prepared by adding a chloroform solution of bromine to a chloroform solution of ethylmercaptoacetone, adding thioacetamide, and heating. 2 : 4-Dimethyl-5-phenylmercaptothiazole, 2 : 4 - dimethyl - 5 - benzthiazolylmercaptothiazole, 2 - methyl - 4 - phenyl - 5 - ethylmercaptothiazole, 2 - amino - 4 - phenyl - 5 - phenylmercaptothiazole, 2 - phenyl-4 - methyl - 5 - ethylmercaptothiazole, 2 - benzyl - 4 - methyl - 5 - phenylmercaptothiazole, and 2 - b  - pyridyl - 4 - phenyl - 5 - phenylmercaptothiazole are similarly prepared.  Compounds of the general formula R1COCH2 SR2 are prepared by reacting a halogenomethylalkyl, aryl, or heterocyclic ketone with a metal salt of a mercaptan.  Ketones specified are chloroacetone, chloromethyl ethyl ketone, chloromethyl propyl ketone, 7-bromo-2-methylheptanone - (6), 4 - bromo - 2 : 2 - dimethylbutanone - 3, chloromethyl - p - tolylketone, bromomethyl - p - tolylketone, chloromethyl-p - methoxyphenyl ketone, bromomethyl p-methoxyphenyl ketone, chloromethyl p-acetoxyphenyl ketone, chloromethyl - p - hydroxyphenyl ketone, chloromethyl o-methoxyphenyl ketone, bromomethyl o-acetoxyphenyl ketone, chloromethyl-1-naphthyl ketone, chloromethyl - 5 - acenaphthyl ketone, 2-chloroacetylthiophene, 2 - bromocetylthiophene, 2-bromacetylfurane, and 2-chloracetylbenzthiazole.  Mercaptans specified are butanethiol - 2, tert. - butylmercaptan, hexylmercaptan, cetyl mercaptan, thioacetic acid, thiomaleic acid, p-phenylthiophenol, 2 : 4-dimethylphenylmercaptan, 2-thionaphthol, benzylmercaptan, 2 - mercaptopyridine, 2 - mercaptothiazoline, 2 - mercaptoimidazole, 3 - mercapto - 1 : 2 : 4 - triazole, 5 - mercaptobarbituric acid, 4-mercaptoquinaldine, 2-mercaptobenzimidazole, 2 - mercapto - 4 : 5 - benzo1 : 3 - thiazine, 8 - mercaptopurine, and 9-mercaptoacridine.  2 - Acetonylmercaptobenzthiazole is prepared by successively adding 2-mercaptobenzthiazole and chloroacetone to a methanol solution of sodium hydroxide.  a -Ethylmercaptoacetophenone is similarly prepared.  2 - a  - Bromoacetonyl - mercaptobenzthiazole is prepared by adding a chloroform solution of bromine to a chloroform solution of 2-acetonylmercaptobenzthiazole.  o  - Bromo - o  - ethylmercaptoacetophenone and o  - bromo - o -phenoxyacetophenone are similarly prepared.  Phenoxyacetophenone is prepared by adding phenacylbromide to an aqueous sodium hydroxide solution of phenol. The Specification as open to inspection under Sect. 91 refers also to the production of the corresponding ether and seleno-ether-substituted thiazoles and selenazoles, and in particular to the preparation of 2-methyl-4-phenyl-5-phenoxythiazole.  This subject-matter does not appear in the Specification as accepted.